CN108199106B - Recovery process of waste materials in production process of nickel-cobalt-manganese ternary precursor - Google Patents
Recovery process of waste materials in production process of nickel-cobalt-manganese ternary precursor Download PDFInfo
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002243 precursor Substances 0.000 title claims abstract description 56
- 239000002699 waste material Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000011084 recovery Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000002386 leaching Methods 0.000 claims abstract description 24
- 238000001556 precipitation Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000012452 mother liquor Substances 0.000 claims abstract description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 35
- 239000000047 product Substances 0.000 claims description 16
- 239000002893 slag Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 14
- 239000002351 wastewater Substances 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 3
- 238000006479 redox reaction Methods 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 11
- 229910052976 metal sulfide Inorganic materials 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012493 hydrazine sulfate Substances 0.000 description 2
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 2
- LIAWOTKNAVAKCX-UHFFFAOYSA-N hydrazine;dihydrochloride Chemical compound Cl.Cl.NN LIAWOTKNAVAKCX-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a recovery process of waste materials in the production process of a nickel-cobalt-manganese ternary precursor, which aims at recovering valuable metals such as unqualified waste materials which fail to meet the product standard, ground reclaimed materials and the like generated in the production process; firstly, carrying out acid dissolution reaction on the nickel-cobalt-manganese ternary precursor waste by using a sulfuric acid solution, leaching acid-decomposable components, then carrying out redox reaction on the valuable metal active sulfide recovered from the nickel-cobalt-manganese ternary precursor precipitation mother liquor and acid-insoluble partial oxide in the nickel-cobalt-manganese ternary precursor waste by using the reducibility of the valuable metal active sulfide, and fully utilizing the redox of the two substances to decompose the nickel-cobalt-manganese ternary precursor waste so as to achieve the aim of recovery. The whole process reaction fully considers the treatment process of combining waste residues and wastewater in the production process, reduces the production cost and improves the recovery rate of valuable metals; the whole process is simple, the number of control points is small, other impurities cannot be introduced in the reaction process, impurity removal procedures are reduced, and impurity removal cost is saved.
Description
Technical Field
The invention relates to the technical field of recycling of nickel-cobalt-manganese ternary precursor wastes, in particular to a process for recycling wastes in a nickel-cobalt-manganese ternary precursor production process.
Background
Since 2014, China has successively developed a new energy automobile related supporting policy, the nickel-cobalt-manganese acid lithium ternary material has the advantages of low cost, high specific capacity, good rate capability, good safety performance and the like as a power battery anode material with the most prospect in the present time, and the market demand of the nickel-cobalt-manganese acid lithium ternary material serving as a front end material of the ternary anode material is increased year by year. Because the coprecipitation process parameters in the production process are not controlled stably, the obtained product can not meet the expected physical property and chemical index requirements, and is called waste in the industry, and the main component of the waste is a mixture of hydroxides or oxides of two or more elements of Co, Ni and Mn.
The existing technical scheme for decomposing the precursor waste is as follows:
the method disclosed in patent No. CN201210228336.4 is: firstly, preparing a dissolving assistant solution, wherein the main component of a cosolvent is one or a mixture of several of sodium sulfite, sodium thiosulfate, SO2 gas, H2S gas, hydrazine hydrate, hydrazine sulfate, hydrazine dihydrochloride, hydrogen peroxide, hydrochloric acid and the like; secondly, pouring the precursor waste into a cosolvent for size mixing to form uniform suspension size; finally, adding concentrated acid into the slurry under the stirring state, and reacting until the suspension is gradually converted into a transparent salt solution; filtering out insoluble slag in the salt solution to obtain the product. The main components of the cosolvent used in the reaction process are one or a mixture of several of sodium sulfite, sodium thiosulfate, SO2 gas, H2S gas, hydrazine hydrate, hydrazine sulfate, hydrazine dihydrochloride, hydrogen peroxide, hydrochloric acid and the like. Furthermore, a sulfuric acid solution having a concentration of 98% is used in the reaction, which is dangerous in handling. Some substances of the substances have high toxicity, and the environmental protection requirements in the processes of use, preservation and recovery of waste water and tail gas are strict.
The method disclosed in patent No. CN201310175586.0 is that firstly, a lithium ion battery anode material or a precursor thereof containing at least one of Co and Mn with the particle size of less than 200 mu m is mixed with water, concentrated sulfuric acid is added to obtain a mixed solution with the concentrated sulfuric acid concentration of 5 mol/L-8.5 mol/L, then the mixed solution is heated to 95-100 ℃, any one of hydrazine hydrate, triethanolamine and polyhydric alcohol is added for reaction for 3-5 times, the reaction time is 5-10 minutes, and a solution containing transition metal ions of at least one of Co and Mn is obtained.
Disclosure of Invention
The invention aims to provide a process for recovering waste materials in the production process of a nickel-cobalt-manganese ternary precursor, which has the advantages of simple operation, easy control, easy storage of reagents used in reaction, low risk, reduction in recovery cost while recovering nickel, cobalt and manganese components and the like, and solves the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a process for recovering waste materials in the production process of a nickel-cobalt-manganese ternary precursor comprises the following steps:
s1: precipitating the mother liquor; precipitating and recycling valuable metal ions remained in the mother liquor after the nickel-cobalt-manganese ternary precursor is precipitated by using soluble sulfides, and controlling the pH value at the precipitation end point to be 7-9;
s2: reacting the nickel-cobalt-manganese ternary precursor waste with a sulfuric acid solution, filtering after the reaction is finished, returning the filtrate as a nickel-cobalt-manganese solution to a precipitation process as a product to continuously produce a nickel-cobalt-manganese ternary precursor, and standing leaching residues for later use;
s3: respectively adding the metal active sulfide obtained in the step S1 and the leaching slag obtained in the step S2 into a prepared sulfuric acid solution for size mixing, heating the prepared size to 80-95 ℃, and carrying out heat preservation reaction for 4-8 hours;
s4: after the reaction is finished, performing precision filtration, periodically cleaning a filter element of the filter, taking the filtrate as a nickel-cobalt-manganese mixed solution, and returning the mixed solution as a product to a precipitation process to continuously produce the nickel-cobalt-manganese ternary precursor.
Preferably, the liquid-solid ratio of the sulfuric acid to the nickel-cobalt-manganese ternary precursor waste in the step S2 is 5:1, the concentration of the sulfuric acid participating in the reaction is 1.0-2.0 mol/L, the reaction temperature is 80-90 ℃, and the reaction time is 2-4 h.
Preferably, the molar ratio of the leaching slag to the metal active sulfide in the reaction of the step S3 is 1: 1-1: 2.5, the concentration of the sulfuric acid solution is 1.5-2.5 mol/L, the liquid-solid ratio in the reaction process is 6: 1-8: 1, the reaction temperature is 80-95 ℃, and the reaction time is 4-8 h.
Preferably, no other impurities are introduced into the nickel-cobalt-manganese solution obtained in the steps S2 and S3 in the whole reaction process, and the obtained solution can be directly returned to the nickel-cobalt-manganese ternary precursor precipitation production process for production, so that the impurity removal cost is reduced.
Preferably, the reducing property of the recycled metal sulfide is utilized to carry out reduction reaction on the oxidation components in the nickel-cobalt-manganese ternary precursor leaching slag in the whole process, and waste residues and waste water generated in the ternary precursor production process are reasonably and effectively comprehensively recycled.
Compared with the prior art, the invention has the beneficial effects that:
the whole process reaction fully considers the treatment process of combining waste residues and wastewater in the production process, reduces the production cost and improves the recovery rate of valuable metals; secondly, the whole process is simple, few in control points and strong in operability, and can be widely used in large-scale production; particularly, no other impurities are introduced into the nickel-cobalt-manganese solution obtained in the steps S2 and S3 in the whole reaction process, the obtained solution can be directly returned to the nickel-cobalt-manganese ternary precursor precipitation production process for production, the impurity removal cost is reduced, and no other impurities are introduced into the whole reaction process. Meanwhile, the reducing property of the recycled metal sulfide is utilized to carry out reduction reaction on the oxidation components in the nickel-cobalt-manganese ternary precursor leaching slag in the whole process, and waste residues and waste water generated in the ternary precursor production process are reasonably and effectively comprehensively recycled.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, in the embodiment of the present invention: a process for recovering waste materials in the production process of a nickel-cobalt-manganese ternary precursor comprises the following steps:
the first step is as follows: precipitating the mother liquor; precipitating and recycling valuable metal ions remained in the mother liquor after the nickel-cobalt-manganese ternary precursor is precipitated by using soluble sulfides, and controlling the pH value at the precipitation end point to be 7-9;
secondly, reacting the nickel-cobalt-manganese ternary precursor waste with a sulfuric acid solution, filtering after the reaction is finished, returning the filtrate as a nickel-cobalt-manganese solution to a precipitation process as a product to continuously produce the nickel-cobalt-manganese ternary precursor, and standing leaching residues for later use, wherein the liquid-solid ratio of the sulfuric acid to the nickel-cobalt-manganese ternary precursor waste during the reaction is 5:1, the concentration of the sulfuric acid participating in the reaction is 1.0-2.0 mol/L, the reaction temperature is 80-90 ℃, and the reaction time is 2-4 h;
thirdly, adding the metal active sulfide obtained in the first step and the leaching residue obtained in the second step into a prepared sulfuric acid solution for size mixing, heating the prepared size to 80-95 ℃, and carrying out heat preservation reaction for 4-8 hours, wherein the molar ratio of the leaching residue to the metal active sulfide in the reaction is 1: 1-1: 2.5, the concentration of the sulfuric acid solution is 1.5-2.5 mol/L, the liquid-solid ratio in the reaction process is 6: 1-8: 1, the reaction temperature is 80-95 ℃, and the reaction time is 4-8 hours;
other impurities are not introduced into the nickel-cobalt-manganese solution obtained in the second step and the third step in the whole reaction process, and the obtained solution can be directly returned to the nickel-cobalt-manganese ternary precursor precipitation production process for production, so that the impurity removal cost is reduced;
the fourth step: after the reaction is finished, performing precision filtration, periodically cleaning a filter element of the filter, taking the filtrate as a nickel-cobalt-manganese mixed solution, and returning the mixed solution as a product to a precipitation process to continuously produce the nickel-cobalt-manganese ternary precursor.
The oxidation components in the nickel-cobalt-manganese ternary precursor leaching slag are subjected to reduction reaction by utilizing the reducibility of the recycled metal sulfide in the whole process, and waste residues and waste water generated in the ternary precursor production process are reasonably, effectively and comprehensively recycled, so that the purposes of emission reduction and environmental protection are achieved.
The first embodiment is as follows:
based on the above description, the following specific examples are provided: for example, the main contents of the nickel-cobalt-manganese ternary precursor waste are as follows: co12.19%, Ni 31.48%; 18.33 percent of Mn;
the method comprises the following steps: precipitating and recycling valuable metals in mother liquor in the production process of the nickel-cobalt-manganese ternary precursor by utilizing sodium sulfide, wherein the content of precipitated metal sulfides is as follows: 0.3 percent of Co; ni 12.66%; mn 12.32%;
secondly, carrying out acid dissolution leaching on the nickel-cobalt-manganese ternary precursor waste by using 1.25 mol/L sulfuric acid solution, wherein the liquid-solid ratio is 5:1, the reaction temperature is 90 ℃, the reaction time is 4 hours, the leaching residue is standby, the filtrate is used as a product solution and is sent to a ternary precursor precipitation process to produce a precursor product, and the main content of the nickel-cobalt-manganese solution is Co 19.85 g/L, Ni 52.73 g/L, Mn 0.004 g/L and PH = 1.13;
step three, weighing the leaching slag and the metal sulfide in the step two, wherein the molar ratio of the leaching slag to the metal sulfide is 1: 1, adding the leaching slag to the metal sulfide together into a 2.0N sulfuric acid solution, the liquid-solid ratio is 6: 1, the reaction temperature is 95 ℃, reacting for 8 hours, wherein basically no slag remains in the reaction, and after precise filtration, the filtrate is used as a product solution to be sent to a ternary precursor precipitation process to produce a precursor product, wherein the main content of the nickel-cobalt-manganese solution is Co 5.92 g/L, Ni 31.8 g/L, Mn 28.63 g/L, and the pH is = 2.21;
step four: the result of the calculation of the leaching rate of the whole reaction is as follows: 99.94 percent of Co; 98.96 percent of Ni; and 99.98 percent of Mn.
Example two:
providing the main content of the nickel-cobalt-manganese ternary precursor waste: 12.19 percent of Co and 31.48 percent of Ni; recovery process of Mn 18.33%:
the method comprises the following steps: precipitating and recycling valuable metals in mother liquor in the production process of the nickel-cobalt-manganese ternary precursor by utilizing sodium sulfide, wherein the content of precipitated metal sulfides is as follows: 0.3 percent of Co; ni 12.66%; mn 12.32%;
secondly, carrying out acid dissolution leaching on the nickel-cobalt-manganese ternary precursor waste by using 1.25 mol/L sulfuric acid solution, wherein the liquid-solid ratio is 5:1, the reaction temperature is 90 ℃, the reaction time is 4 hours, the leaching residue is standby, the filtrate is used as a product solution and is sent to a ternary precursor precipitation process to produce a precursor product, and the main content of the nickel-cobalt-manganese solution is Co 19.85 g/L, Ni 52.73 g/L, Mn 0.004 g/L and PH = 1.13;
step three, weighing the leaching slag and the metal sulfide in the step two, adding the leaching slag and the metal sulfide together into a 2.5N sulfuric acid solution according to the mol ratio of 1: 2, wherein the liquid-solid ratio is 8: 1, the reaction temperature is 95 ℃, the reaction is carried out for 8 hours, the reaction basically has no slag residue, and after precise filtration, the filtrate is used as a product solution to be sent to a hydroxide precursor precipitation process to produce a precursor product, wherein the main content of the nickel-cobalt-manganese solution is Co 4.91 g/L, Ni 28.42 g/L, Mn 25.45 g/L, and the pH is = 1.66;
step four: the result of the calculation of the leaching rate of the whole reaction is as follows: 99.81 percent of Co; ni 97.51%; mn 97.09%.
In summary, the following steps: according to the recovery process of the waste materials in the production process of the nickel-cobalt-manganese ternary precursor, the whole process reaction fully considers the treatment process of combining waste residues and waste water in the production process, so that the recovery rate of valuable metals is improved while the production cost is reduced; secondly, the whole process is simple, few in control points and strong in operability, and can be widely used in large-scale production; in addition, other impurities are not introduced in the reaction process, impurity removal procedures are reduced, the obtained nickel-cobalt-manganese mixed solution is low in impurity content, and the method can be directly applied to the production process of nickel-cobalt-manganese hydroxide precursors, and saves impurity removal cost.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (1)
1. The process for recycling the waste materials in the production process of the nickel-cobalt-manganese ternary precursor is characterized by comprising the following steps of:
s1: precipitating the mother liquor; precipitating and recycling valuable metal ions remained in the mother liquor after the nickel-cobalt-manganese ternary precursor is precipitated by using soluble sulfides, and controlling the pH value at the end point of precipitation to be 7-9;
s2: reacting the nickel-cobalt-manganese ternary precursor waste with a sulfuric acid solution, filtering after the reaction is finished, returning the filtrate as a nickel-cobalt-manganese solution to a precipitation process as a product to continuously produce a nickel-cobalt-manganese ternary precursor, and standing leaching residues for later use;
s3: respectively adding the metal active sulfide obtained in the step S1 and the leaching slag obtained in the step S2 into a prepared sulfuric acid solution for size mixing, heating the prepared size to 80-95 ℃, and carrying out heat preservation reaction for 4-8 hours;
s4: after the reaction is finished, performing precision filtration, periodically cleaning a filter element of a filter, taking the filtrate as a nickel-cobalt-manganese mixed solution, and returning the mixed solution as a product to a precipitation process to continuously produce a nickel-cobalt-manganese ternary precursor;
in the step S2, the liquid-solid ratio of the sulfuric acid to the nickel-cobalt-manganese ternary precursor waste material during reaction is 5:1, the concentration of the sulfuric acid participating in the reaction is 1.0-2.0 mol/L, the reaction temperature is 80-90 ℃, and the reaction time is 2-4 h;
the molar ratio of the leaching slag to the metal active sulfide in the reaction of the step S3 is 1: 1-1: 2.5, the concentration of the sulfuric acid solution is 1.5-2.5 mol/L, the liquid-solid ratio in the reaction process is 6: 1-8: 1, the reaction temperature is 80-95 ℃, and the reaction time is 4-8 hours.
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